Crosslinked and crosslinkable hollow fiber mixed matrix membrane and method of making same

ABSTRACT

A composition of and a method of making high performance mixed matrix hollow fiber membranes is described. The membranes have a high resistance to plasticization by use of a predetermined amount of crosslinking. The preferred polymer material for the membrane is a polyimide polymer contineous phase comprising ester crosslinks and a molecular sieve material dispersed within the polymer contineous phase. The resultant mixed matrix hollow fiber membrane exhibits a high permeability of CO 2  in combination with a high CO 2 /CH 4  selectivity. Another embodiment provides a method of making the mixed matrix hollow fiber membrane from a monesterified polymer followed by final crosslinking after hollow fiber formation.

FIELD OF THE INVENTION

[0001] The present invention relates to the separation of mixtures using polymer membranes.

BACKGROUND

[0002] Polymer membranes have been proposed for various separations. It has been found that different molecules can be made to diffuse through selected polymers differently. For example if one component of a mixture is found to diffuse though a polymer rapidly and a second component is found to diffuse through the polymer very slowly or not at all, the polymer may be utilized to separate the two components. Polymer membranes potentially can be used for gas separations as well as liquid separations.

[0003] Polymeric membrane materials have been found to be of use in gas separations. Numerous research articles and patents describe polymeric membrane materials (e.g., polyimides, polysulfones, polycarbonates, polyethers, polyamides, polyarylates, polypyrrolones, etc.) with desirable gas separation properties, particularly for use in oxygen/nitrogen separation (See, for example, Koros et al., J. Membrane Sci., 83, 1-80 (1993), the contents of which are hereby incorporated by reference, for background and review).

[0004] The polymeric membrane materials are typically used in processes in which a feed gas mixture contacts the upstream side of the membrane, resulting in a permeate mixture on the downstream side of the membrane with a greater concentration of one of the components than the composition of the original feed gas mixture. A pressure differential is maintained between the upstream and downstream sides, providing the driving force for permeation. The downstream side can be maintained as a vacuum, or at any pressure below the upstream pressure.

[0005] The membrane performance is characterized by the flux of a gas component across the membrane. This flux can be expressed as a quantity called the permeability (P), which is a pressure- and thickness-normalized flux of a given component. The separation of a gas mixture is achieved by a membrane material that permits a faster permeation rate for one component (i.e., higher permeability) over that of another component. The efficiency of the membrane in enriching a component over another component in the permeate stream can be expressed as a quantity called selectivity. Selectivity can be defined as the ratio of the permeabilities of the gas components across the membrane (i.e., P_(A)/P_(B), where A and B are the two components). A membranes permeability and selectivity are material properties of the membrane material itself, and thus these properties are ideally constant with feed pressure, flow rate and other process conditions. However, permeability and selectivity are both temperature-dependent. It is desired to develop membrane materials with a high selectivity (efficiency) for the desired component, while maintaining a high permeability (productivity) for the desired component.

[0006] The relative ability of a membrane to achieve the desired separation is referred to as the separation factor or selectivity for the given mixture. There are however several other obstacles to use of a particular polymer to achieve a particular separation under any sort of large scale or commercial conditions. One such obstacle is permeation rate. One of the components to be separated must have a sufficiently high permeation rate at the preferred conditions or else extraordinarily large membrane surface areas are required to allow separation of large amounts of material. Another problem that can occur is that at conditions where the permeability is sufficient, such as at elevated temperatures or pressures, the selectivity for the desired separation can be lost or reduced. Another problem that often occurs is that over time the permeation rate and/or selectivity is reduced to unacceptable levels. This can occur for several reasons. One reason is that impurities present in the mixture can over time clog the pores, if present, or interstitial spaces in the polymer. Another problem that can occur is that one or more components of the mixture can alter the form or structure of the polymer membrane over time thus changing its permeability and/or selectivity. One specific way this can happen is if one or more component of the mixture causes plasticization of the polymer membrane. Plasticization occurs when one or more of the components of the mixture acts as a solvent in the polymer often causing it to swell and lose its membrane properties. It has been found that polymers such as polyimides which have particularly good separation factors for separation of mixtures comprising carbon dioxide and methane are prone to platicization over time thus resulting in decreasing performance of the membranes made from the polyimides.

[0007] The present invention overcomes some of the problems of the prior art membranes by providing a polymer membrane and a method of making said polymer membrane that has the following properties/ advantages:

[0008] a) Excellent selectivity and permeability,

[0009] b) Sustained selectivity over time by resistance to plasticization, and

[0010] c) Very large useable surface area by use of hollow fibers.

SUMMARY

[0011] As discussed above the present invention seeks to provide a membrane and method of making the membrane that achieves the result of providing a commercially viable polymer membrane that overcomes some of the drawbacks of the prior art membranes. The membranes of the present invention can have very large available surface areas using hollow fiber technology. The membranes of the present invention also have a very high selectivity at a very high permeability. The membranes of the present invention also are quite resistant to plasticization and maintain their selectivity and permeability properties over time as is required in commercial applications of this technology. The membrane of the present invention achieves this result by providing a predetermined number crosslinkable sites in the polymer chain and by crosslinking the polymer membrane using selected crosslinkers. The crosslinkable polymer and crosslinked polymer is achieved without degradation of the imide function (i.e. without altering the polyimide structure.)

[0012] In one embodiment of the present invention a hollow fiber mixed matrix polymer membrane is provided, comprising; a crosslinked polymer continuous phase, and a molecular sieve material dispersed within the polymer continuous phase. The resulting membrane can have a CO₂ permeability of at least 20 barrers and a CO₂/CH₄ selectivity of greater than 30, when measured at 35 degrees C. and a pressure of 100 psia.

[0013] In an alternative embodiment of the present invention a hollow fiber mixed matrix polymer membrane is provided, comprising: a crosslinked polyimide polymer continuous phase and a molecular sieve material dispersed within the polymer continuous phase having a ratio of crosslinkable sites to imide groups of between 3:8 and 1:16. It has been found that too much crosslinking can cause the hollow fiber polymer to be fragile and can also experience performance problems. Too little crosslinking can lead to plasticization of the polymer membrane over time resulting in deteriorating performance and loss of selectivity.

[0014] In another alternative embodiment of the present invention a hollow fiber mixed matrix polymer membrane is provided, comprising a molecular sieve dispersed within a continuous polymer phase wherein said continuous polymer phase comprises a polyimide polymer made from the monomers A+B+C;

[0015] where A is the dianhydride of the formula;

[0016] where X₁ and X₂ are the same or different halogenated alkyl group, phenyl or halogen;

[0017] where R₁, R₂, R₃, R₄, R₅, and R₆ are H, alkyl, or halogen;

[0018] where B is a diamino cyclic compound without a carboxylic acid functionality;

[0019] where C is a diamino cyclic compound with a carboxylic acid functionality; and

[0020] wherein the ratio of B to C is between 1:4 and 8:1.

[0021] A particularly preferred embodiment of the present invention relates to using the crosslinked mixed matrix hollow fiber polymer membrane of the present invention for the separation of carbon dioxide (CO₂) from methane (CH₄). In particular this embodiment of the invention relates to the removal of CO₂ from natural gas comprising CO₂, CH₄, and other light gasses.

[0022] Among other factors the present invention provides the composition of and the method of making a highly effective polymeric membrane for the separation of mixtures. The invention utilizes crosslinking of the mixed matrix polymer membrane to help achieve the high selectivity required to make the separation efficiently and to maintain the high selectivities and other properties even after being exposed to extreme conditions such as high temperatures and pressures. The invention also shows that plasticization of the mixed matrix polymer membrane can be avoided by appropriate degrees of crosslinking and appropriate selection of the crosslinking units. It has also been determined that too much crosslinking can lead to hollow fibers that are brittle and subject to failure. The present invention has thus achieved a hollow fiber polymer membrane that is both highly selective and highly permeable for the preferred separations while also being stable and durable for long term use in a commercial separation process at actual working conditions. The present invention also provides a method of making a mixed matrix hollow fiber polymer membrane precursor material that is not excessively fragile allowing effective spinning.

[0023] A preferred method for preparing hollow fibers is to dissolve the polymer in a solvent or melt the polymer, and extrude the polymer through a tubular capillary nozzle with a core fluid used for the purpose of retaining the hollow fiber shape.

[0024] Any mixture of fluids that differ in size or other properties, for example nitrogen and oxygen or ethylene and ethane, may be separated using the membranes described herein. In one embodiment, a gaseous mixture containing methane and carbon dioxide can be enriched in methane by a gas-phase process through the membrane. In other embodiments, the membranes can be used to purify helium, hydrogen, hydrogen sulfide, oxygen and/or nitrogen.

BRIEF DESCRIPTION OF THE DRAWINGS

[0025]FIG. 1 shows the Monoesterification and Transesterification Reactions.

[0026]FIG. 2 shows the synthesis of the monoester via the acid chloride copolyimide route.

[0027]FIG. 3 is a proton NMR of an uncrosslinked polymer (pre-esterification).

[0028]FIG. 4 is a proton NMR of the same polymer as FIG. 3 that has been monoesterified with 1,4-butanediol.

[0029]FIG. 5 is a proton NMR of a polymer that has been monoesterified with ethylene glycol.

[0030]FIG. 6 is a Single Fiber Test Module.

[0031]FIG. 7 is a permeation testing system for membrane fiber modules.

[0032]FIG. 8 shows the CO₂ permeability at increasing pressures for a crosslinked material.

[0033]FIG. 9 shows the CO₂ permeability at increasing pressures for a uncrosslinked material.

DETAILED DESCRIPTION OF THE INVENTION

[0034] The present invention relates to a highly durable mixed matrix hollow fiber membrane exhibiting both high permeability of CO₂ and high CH₄/CO₂ selectivity and being resistant to plasticization. Prior membranes have shown a significant decline in selectivity over time. Not to be limited by theory it is believed that the selectivity losses associated with exposure to high levels of CO₂ are the result of plasticization. Carbon dioxide acts as a strong swelling agent, sorbing into the polymer matrix and greatly increasing segmental motion. This increased motion drastically reduces the difference in diffusion rates between fast and slow gas species. If this swelling and segmental motion could be limited, the selectivity of the membrane can be maintained. In the present invention crosslinking has been shown to reduce or eliminate CO₂ plasticization in dense films. Proper selection of the method of crosslinking, the chemical structure of the polymer and crosslink, and proper degree of crosslinking are important to achieve a hollow fiber membrane that achieves and maintains superior permeability and selectivity need for a viable commercial membrane.

[0035] U.S. Pat. No. 5,288,304 teaches generally a method for preparation of carbon molecular sieve membranes. That disclosure is incorporated herein by reference in its entirety. Patents that relates to the separation of fluids by means of a mixed matrix or composite membrane are U.S. Pat. Nos. 4,740,219 and 4,925,459 which are incorperated herein by reference in their entirety. A copending U.S. patent application that discloses a Process for CO₂/Natural Gas Separation is U.S. Pat. No. 6,299,668 is incorporated herein by reference.

[0036] The polyimide is derived from a reaction of any suitable reactants. Reactants can include monomers such as dianhydrides, as well as tetra carboxylic acids, and furandiones. Other monomers include diamino compounds, preferably diamino cyclic compounds, still more preferably diamino aromatics. The diamino aromatics can include aromatic compounds having more than one aromatic ring where the amino groups are on the same or different aromatic ring. In the present invention it is also important for the polyimide to have incorporated in it a predetermined amount of crosslinkable sites. These sites may include but are not limited to carboxylic acid sites, ester functions, —OH groups, unreacted NH₂ groups, —SH groups, amide functions, and olefins. The preferred crosslinkable sites in the process of the present invention are carboxylic acid or ester groups, alcohols, and olefins. Crosslinking can also be induced by reaction of the imide function itself to form a crosslinkable site and an amide. This method of crosslinking will be discussed in more detail later. Another preferred feature of the process of the present invention is that the polyimide chains have limited rotational ability. One such monomer that provides a polyimide chain with limited rotational ability is:

[0037] This dianhydride is known as 6FDA or 4,4′-(hexafluoroisopropylidene) diphthalic anhydride, or (2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride.

[0038] In the process of the present invention a carboxylic acid functionality is intended to include the acid group itself as well as acid derivatives such as esters and anhydrides as well as activated carboxylic acid derivatives such as acid chlorides.

[0039] A preferred monomer for providing the carboxylic acid functionality in the present invention is diamino benzoic acid:

[0040] A particularly preferred monomer is 3,5 diaminobenzoic acid.

[0041] The diamino cyclic compounds without a carboxylic acid functionality can include aromatic compounds having more than one aromatic ring where the amino groups are on the same or different aromatic ring. Preferred examples include but are not limited to 4,4′ isopropylidene dianiline, 3,3′ hexafluoroisopropylidene dianiline, 4,4′ hexafluoroisopropylidene dianiline, 4,4′ oxydianiline, 3,3′ oxydianiline and 4,4′ diaminodiphenyl. Examples of diamino aromatic compounds useful in the present invention include diaminotoluene, diaminobenzotrifluoride, and di, tri, and tetramethyidiaminobenzene.

[0042] The polymer membranes of the present invention can be used for gas/gas separations, gas/liquid separations, liquid/liquid separations, and liquid/solid separations.

[0043] As mentioned above one of the preferred crosslinkable sites comprise carboxylic acid or esters or activated carboxylic acid derivitives. Crosslinking groups or agents that have been found to be useful in conjunction with the carboxylic acid functional sites include: diols selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,2 butanediol, benzenedimethanol, and 1,3 butanediol. Preferred crosslinking agents include ethylene glycol, propylene glycol, 1,3 propanediol, and benzenedimethanol. Still more preferred crosslinking agents are ethylene glycol, and 1,3 propanediol. It has been found that having too long a crosslinking group can have an undesirable impact on the permeability and/or selectivity of the polymer however too short a crosslink can also have a negative on the finished hollow fiber membrane. The most preferred crosslinking agents for crosslinking carboxylic acid or ester sites is 1,3 propanediol.

[0044] Crosslinking can occur by the condensation reaction of selected diol or diols with the crosslinkable acid functionality. In the process of the present invention it has been found that reaction of less reactive crosslinking agents can be facilitated by activation of the carboxylic acid site on the polymer chain. One way to do this is by converting the acid group to the corresponding acid chloride. This can be effectively done by the use of thionyl chloride. A method for this activation will be discussed in more detail in the examples.

[0045] In a preferred embodiment of the process of the present invention crosslinking can be achieved in a stepwise fashion by first monoesterification of the acid function with the selected diol or diols, followed by transesterification of the monoester to the diester. (See FIG. 1)

[0046] In a particularly preferred embodiment of the present invention the monoesterified polymer is spun into the hollow fiber prior to transesterification to form the crosslinked hollow fiber membrane. There are significant advantages to this process in particular the monoester polymer can be more easily spun without breaking or forming defects.

[0047] Alcohol or —OH groups can provide crosslinkable sites in the present invention. Crosslinking groups useable with alcohol crosslinkable sites include dicarboxylic acids, anhydrides, and diesters. Examples of dicarboxylic acids useful as crosslink groups include but are not limited to oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, and adipic acid. Non limiting examples of anhydrides that may be used include maleic anhydride, succinic anhydride, and methylsuccinic anhydride. Non limiting examples of diesters are dimethylterephthalate, dimethylisophthalate, dimethylphthalate, and diesters of the dicarboxylic acids mentioned above. The dicarboxylic acids and anhydrides can be reacted with the -OH containing polyimide at esterification to form a crosslink. Likewise the diesters discussed above can subjected to transesterification conditions in the presence of the —OH containing polyimide to form the desired ester crosslink.

[0048] In a preferred embodiment of the present invention the —OH containing polyimide is subjected to monoesterification conditions in the presence of one or more of the crosslinking groups to form a monoesterified polyimide. It has been found that the monoesterified polyimide can then be made into a hollow fiber as described in detail later in this patent application. The hollow fiber can then be subjected to transesterification conditions after hollow fiber formation to form the crosslinked hollow fiber polymer membrane.

[0049] Examples of reactants that can be used to provide a —OH containing polyimide include diaminobenzyl alcohol, diaminocyclohexanol, and other diaminoalcohols.

[0050] In some cases it may be preferable to protect the —OH function prior to formation of the polyimide. This may be done by conventional chemical means such as by masking the -OH group off as an ether. The masked —OH group may then be hydrolyzed back to a functional —OH group prior to crosslinking or prior to the extrusion of the hollow fiber.

[0051] Also mentioned above are crosslinkable sites comprising olefins. Crosslinking groups useable with olefins include but are not limited to sulfur, divinylbenzene. Sulfur as a crosslinking agent is thought to form a disulfide crosslink when reacted with an olefin.

[0052] A particularly preferred diamino group that can be used to make a crosslinkable polyimide polymer is diaminobenzoic acid (DABA). The most preferred isomer of DABA is 3,5 diaminobenzoic acid.

[0053] In an alternative embodiment of the present invention a crosslinking-like effect can be achieved simply by the presence of crosslinkable groups in the polymer chain. Crosslinkable groups such as carboxylic acid functions can have an effect very similar to actual covalent crosslinking. This effect can be referred to as pseudocrosslinking. Not to be limited by theory pseudocrosslinking is thought to occur because the crosslinkable groups can provide a weak attractive interaction between polymer chains that behaves similarly to actual crosslinking. The interaction can be a weak ionic bond, hydrogen bond or Van der Waals forces. These weak interactions cause the polymer to be weakly crosslinked.

[0054] In another alternative embodiment of the present invention only a fraction of the available crosslinkable sites are actually crosslinked. In this embodiment the resultant polymer membrane has a combination of true crosslinks and pseudocrosslinks. Such a combination can have processing and durability advantages.

[0055] In yet another embodiment of the present invention the crosslinkable sites are selected such that some of said sites interact with the molecular sieve material such that a weak bond is formed between the polymer and the sieve via the crosslinkable sites. In this way the crosslinkable site serves at least two roles. It provides a site to facilitate crosslinking of the polymer chains and it aids in making the polymer more compatible with the molecular sieve. Thus the crosslinkable group acts as a self primer.

[0056] Molecular Sieve Selection

[0057] One type of molecular sieving entity or particles useful in the present invention is a carbon-based molecular sieve. The molecular sieves used in the mixed matrix membranes described herein are can be prepared by pyrolyzing polymeric particles. Alternatively, the molecular sieve particles may first be prepared by pyrolyzing a polymeric film or other continuous polymeric body. For large scale production of carbon molecular sieve particles, it is more difficult to form and subsequently pyrolyze polymeric films than to use a powdered polymer as the material to be pyrolyzed. U.S. Pat. No. 4,685,940, the contents of which are hereby incorporated by reference in their entirety, discloses carbon membranes for use in separation processes. The polymer used to prepare the carbon membrane can be used to prepare the powder used herein to prepare the molecular sieves particles that are incorporated into the mixed matrix membranes. The resulting particles have a predetermined pore size and function as molecular sieves. Particles formed from the pyrolyzed polymer function well even at elevated temperatures. The carbon particles are ideally produced by the controlled pyrolysis of a suitable powder of polymeric material under conditions that retain the basic integrity of the original geometry. If the powder is not already in the right size range, the pyrolyzed material is milled to a desired size range.

[0058] Suitable materials include polyimides, polyamides, cellulose and derivatives thereof, thermosetting polymers, acrylics, pitch-tar mesophase, and the like. These materials are not limiting, as other materials may be useful for fabricating carbon membranes. Selection of the polymeric material for use in preparing a powder to be pyrolyzed to form sieve particles may be made on the basis of the heat resistance, solvent resistance, and mechanical strength of the porous separation membrane, as well as other factors dictated by the operating conditions for selective permeation. Especially preferred carbon molecular sieve particles are those prepared from the pyrolysis of aromatic polyimides or cellulosic polymers. Examples of aromatic polyimides are described, for example, in U.S. Pat. Nos. 5,234,471 and 4,690,873. Other patents describing useful polymers which can be subjected to pyrolysis include European Patent Application 0 459 623. The contents of each of these patents are hereby incorporated by reference.

[0059] The pyrolysis can be generally effected in a wide range of temperatures, between the decomposition temperature of the carbonaceous material and the graphitization temperature (about 3000° C.). Generally, pyrolysis will be effected in the range of from 250 to 2500° C., a preferred range being about 450 to about 800° C.

[0060] The carbon membranes contain pores larger than the ultramicropores required for the molecular sieving process. It is believed that these larger pores connect the ultramicropores that perform the molecular sieving process and allow for high productivities in the dry membrane state. Generally, the higher the final temperature used for the pyrolysis of the polymer, the smaller the pores of the product, and thus the smaller the molecules that can permeate through such membranes.

[0061] The pyrolysis of suitable precursors, generally under conditions conventionally used for the production of carbon fibers, results in a product that has a certain microporosity of molecular dimensions which is responsible for the molecular sieve properties of the carbons.

[0062] During the pyrolysis process, the heating is preferably effected under a vacuum or inert gas (e.g., nitrogen, argon) atmosphere. Controlled thermal degradation of the polymer precursor results in a pore opening, and thus pre-determined pore-size ranges can be obtained, suitable for the intended separation process.

[0063] For the intended use, it is advantageous to obtain fluid separation membranes having pore size and a pore size distribution that effectively separate specific mixtures of fluids. Generally, a pore size distribution of 3-10 Angstroms is suitable and 3-5 Angstroms is preferable for gas separations.

[0064] The carbon molecular sieves (CMS) or particles of the present invention are believed to be nano- and microporous materials that have distributions of pore sizes and interconnected channels that enable fast transport of gas molecules. Within the distribution of pore sizes are constricted, ultramicroporous pore openings with dimensions that are of the same order of magnitude as molecular sizes of gas molecules. It is generally believed that “ultramicropores” (less than 5 Angstroms) perform the molecular sieving (size-selective) process in carbon molecular sieve materials, while larger “micropores” (6 to 10 Angstroms) connecting ultramicropores provide sorption cavities and allow for high fluxes of gas penetrants by promoting larger average diffusional jumps. Thus, the porous nature of carbon molecular sieves of the present invention provides their capability for high gas permeabilities, yet their molecular sieving morphology permits precise discrimination of gas penetrants to yield highly selective membranes.

[0065] Zeolites are another class of molecular sieve that can be used in making the mixed matrix membranes of the present invention. Small, medium, and large pore zeolites can be used in mixed matrix membranes depending on the intended separation. In the lists that follow zeolite structure types will be identified by their structure type code as assigned by the IZA Structure Commisission following the rules set up by the IUPAC Commission on Zeolite Nomenclature. Each unique framework topology is designated by a structure type code consisting of 3 capital letters.

[0066] Examples of useful small pore size zeolites include but are not limited to the following types:

[0067] ABW, AEI, AFT, AFX, APC, APD, ATN, ATT, ATV, AWW, BIK, BRE, CAS, CHA, DDR, EAB, EDI, ERI, GIS, GOO, ITE, JBW, KFI, LEV, LTA, MER, MON, NAT, PAU, PHI, RHO, RTE, RTH, THO, VNI, YUG, ZON. Examples of specific small pore zeolites that can be used are Linde Type A, Chabazite, Erionite, and SAPO-56.

[0068] Medium pore zeolite types that may be used in the process of the present invention include but are not limited to:

[0069] AEL, AFO, AHT, CGF, DAC, EPI, EUO, FER, HEU, LAU, MEL, MFI, MFS, MTT, NES, PAR, SFF, STF, STI, TER, TON, WEI, and WEN.

[0070] Examples of specific useful intermediate pore size zeolites include but are not limited to ZSM-5, ZSM-1 1, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SUZ-4, SSZ-23; SSZ-25, SSZ-28, SSZ-32, SSZ-36, NU-87, and silicalite. ZSM-5 is described in U.S. Pat. No. Re. 29,948 (of original U.S. Pat. No. 3,702,886). ZSM-11 is described in U.S. Pat. No. 3,709,979. ZSM-22 is described in U.S. Pat. No. 4,556,477. ZSM-23 is described in U.S. Pat. No. 4,076,842. ZSM-35 is described in U.S. Pat. No. 4,016,245. ZSM48 is described in U.S. Pat. No. 4,585,747. SUZ-4 is described in EP Application No. 353,915. SSZ-23 is described in U.S. Pat. No. 4,859,422. SSZ-25 is described in U.S. Pat. Nos. 4,827,667 and 5,202,014. SSZ-28 is described in U.S. Pat. No. 5,200,377. SSZ-32 is described in U.S. Pat. No. 5,053,373. SSZ-36 is described in U.S. Ser. No. 60/034,252. Silicalite is a hydrophobic crystalline silica-based molecular sieve which has been developed and patented (see U.S. Pat. No. 4,061,724) to Gross et al.). A detailed discussion of silicalite may be found in the article “Silicalite, A New Hydrophobic Crystalline Silica Molecular Sieve”; Nature, Vol. 271, Feb. 9, 1978, incorporated herein by reference. The entire contents of all these patents and patent applications are incorporated herein by reference.

[0071] Large pore zeolite types that may be used in the process of the present invention include but are not limited to:

[0072] AFI, AFR, AFS, AFY, ATO, ATS, BEA, BOG, BPH, CAN, CON, CZP, DFO, EMT, FAU, GME, LTL, MAZ, MEI, MOR, MTW, OFF, OSI, RON, SAO, and VET.

[0073] Examples of specific useful intermediate pore size zeolites include but are not limited to Linde Type L, Beta zeolite, CIT-1, Faujasite, Mazzite, Mordenite, ZSM-12, and Offretite.

[0074] Very large pore zeolite types that may be used in the process of the present invention include but are not limited to:

[0075] CLO, VFI, AET, and CFI.

[0076] Specific examples of very large pore zeolites include Cloverite and CTI-5.

[0077] Cation modification of zeolites can be used to affect the separation characteristics of the zeolite. Such cation modification includes ion exchange where sodium or potassium ions in the zeolite are replaced with other ions such as barium, calcium, cesium, or any other selected exchangeable ion. This can be done to adjust the adsorption characteristics of the zeolite thus increasing the selectivity.

[0078] The average particle size of the molecular sieve useful in the present invention is less than 5 microns, more preferably less than 1 micron, still more preferably less than 0.1 microns. Smaller particle size facilitates bonding between the molecular sieve and the polymer. The zeolite particle size can be reduced after synthesis such as by high shear wet milling. Prior to membrane formation, the zeolite may be silanated, either during wet milling or separately.

[0079] It is believed that silanation permits improved bonding between the zeolite outer surface and the polymer. Suitable silane compounds include 3-aminopropyldimethylethoxysilane and 3-isocyanopropyldimethylchlorosilane. Silanation can be carried out, for example, by mixing the zeolite in an ethanol/water mixture containing the silane compound for a period of time (a few minutes up to a few hours), then recovering the treated zeolite and washing with ethanol to remove excess silane.

[0080] Other types of molecular sieves that are useable in the present invention include borosilicate, silico-aluminophosphate (SAPO), aluminophosphate (ALPO), and other zeolite-like molecular sieves. These zeolite-like molecular sieves can have structures similar to the aluminosilicate zeolites discussed above.

[0081] Polymer Selection

[0082] An appropriately selected polymer can be used which permits passage of the desired gases to be separated, for example carbon dioxide and methane. Preferably, the polymer permits one or more of the desired gases to permeate through the polymer at different diffusion rates than other components, such that one of the individual gases, for example carbon dioxide, diffuses at a faster rate through the polymer. In a preferred embodiment, the rate at which carbon dioxide passes through the polymer is at least 10 times faster than the rate at which methane passes through the polymer.

[0083] It is preferred that the membranes exhibit a carbon dioxide/methane selectivity of at least about 5, more preferably at least about 10, and most preferably at least about 30. Preferably, the polymer is a rigid, glassy polymer as opposed to a rubbery polymer or a flexible glassy polymer. Glassy polymers are differentiated from rubbery polymers by the rate of segmental movement of polymer chains. Polymers in the glassy state do not have the rapid molecular motion that permit rubbery polymers their liquid-like nature and their ability to adjust segmental configurations rapidly over large distances (>0.5 nm). Glassy polymers exist in a non-equilibrium state with entangled molecular chains with immobile molecular backbones in frozen conformations. The glass transition temperature (Tg) is the dividing point between the rubbery or glassy state. Above the Tg, the polymer exists in the rubbery state; below the Tg, the polymer exists in the glassy state. Generally, glassy polymers provide a selective environment for gas diffusion and are favored for gas separation applications. Rigid, glassy polymers describe polymers with rigid polymer chain backbones that have limited intramolecular rotational mobility and are often characterized by having high glass transition temperatures (Tg>150° C.).

[0084] In rigid, glassy polymers, the diffusive selectivity tends to dominate, and glassy membranes tend to be selective in favor of small, low-boiling molecules. The preferred membranes are made from rigid, glassy polymer materials that will pass carbon dioxide preferentially over methane and other light hydrocarbons. Such polymers are well known in the art and are described, for example, in U.S. Pat. Nos. 4,230,463 to Monsanto and 3,567,632 to DuPont. Suitable membrane materials include polyimides, polysulfones and cellulosic polymers among others.

[0085] Examples of suitable polymers useable as either the membrane material or the porous support include substituted or unsubstituted polymers and may be selected from polysulfones; poly(styrenes), including styrene-containing copolymers such as acrylonitrilestyrene copolymers, styrene-butadiene copolymers and styrene-vinylbenzylhalide copolymers; polycarbonates; cellulosic polymers, such as cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, nitrocellulose, etc.; polyamides and polyimides, including aryl polyamides and aryl polyimides; polyethers; polyetherimides; polyetherketones; polyethersulfones; poly(arylene oxides) such as poly(phenylene oxide) and poly(xylene oxide); poly(esteramide-diisocyanate); polyurethanes; polyesters (including polyarylates), such as polyethylene terephthalate, poly(alkyl methacrylates), poly(acrylates), poly(phenylene terephthalate), etc.; polypyrrolones; polysulfides; polymers from monomers having alpha-olefinic unsaturation other than mentioned above such as poly (ethylene), poly(propylene), poly(butene-1), poly(4-methyl pentene-1), polyvinyls, e.g., poly(vinyl chloride), poly(vinyl fluoride), poly(vinylidene chloride), poly(vinylidene fluoride), poly(vinyl alcohol), poly(vinyl esters) such as poly(vinyl acetate) and poly(vinyl propionate), poly(vinyl pyridines), poly(vinyl pyrrolidones), poly(vinyl ethers), poly(vinyl ketones), poly(vinyl aldehydes) such as poly(vinyl formal) and poly(vinyl butyral), poly(vinyl amides), poly(vinyl amines), poly(vinyl urethanes), poly(vinyl ureas), poly(vinyl phosphates), and poly(vinyl sulfates); polyallyls; poly(benzobenzimidazole); polyhydrazides; polyoxadiazoles; polytriazoles; poly (benzimidazole); polycarbodiimides; polyphosphazines; etc., and interpolymers, including block interpolymers containing repeating units from the above such as terpolymers of acrylonitrile-vinyl bromide-sodium salt of para-sulfophenylmethallyl ethers; and grafts and blends containing any of the foregoing. Typical substituents providing substituted polymers include halogens such as fluorine, chlorine and bromine; hydroxyl groups; lower alkyl groups; lower alkoxy groups; monocyclic aryl; lower acyl groups and the like.

[0086] Preferred polymers useable in the hollow fiber membrane of the present invention include polyimides. poyletherimides, polyethersulfones and polysulfones. More preferred polymers useable in the membrane material of present invention include polyimides. poyletherimides, and polysulfones made using analogs of 6FDA. Particularly preferred polyimides useable in the present invention comprise polyimides or polyetherimides made using 6FDA.

[0087] In a particularly preferred embodiment of the present invention the hollow fiber polymer membrane is a composite material comprising a membrane layer comprising an effective skin layer as well as a porous support. The porous support material can be the same or different polymer as the membrane. Ideally the porous support is an inexpensive porous polymer. In a composite hollow fiber polymer membrane the porous support layer can be either the inside layer or the outside layer. Most preferably the porous support layer is the inside layer in this embodiment and the “skin” layer is on the outside of the hollow fiber. A composite membrane material is discussed in copending U.S. patent applications Ser. Nos. 09/834,857 and 09/834,808 which are incorporated herein in their entirety. A Patent that discusses composite membranes is U.S. Pat. No. 4,925,459 which is also incorporated herein by reference in its entirety.

[0088] Molecular Weight of the Polymer

[0089] Another parameter that needs to be controlled in order to achieve the high permeability, high selectivity hollow fiber membrane of the present invention is the molecular weight of the polymer material. Molecular weight of the polymer material can be critical to forming a hollow fiber membrane that is not too brittle and has an effective skin layer. Molecular weight of the polymer material can also be critical in achieving a spinnable dope solution. A feature of the present invention is that the selection of polymer having a proper molecular weight (MW) can be important in the formation of a hollow fiber membrane. It is preferable to have a MW above the entanglement molecular weight of the polymer. It has been found that if the molecular weight of the polymer is too low the polymer is too brittle and a effective skin layer may not form. If the molecular weight is too high processability can become difficult. In the present invention it is preferable to have an average polymer molecular weight of between 40,000 and 200,000, more preferably between 60,000 and 160,000, still more preferably between 70,000 and 140,000, and most preferably between 80,000 and 120,000. Not to limited by theory is thought that the MW of the polymer should be above, ideally well above, the entanglement MW of the polymer in order to achieve a material that has high strength and is not brittle. A paper that discusses the effect of molecular weight on polymer properties such as entanglement is in Fundamental Principles of Polymeric Materials, SPE Monograph Series 2^(nd) ed., John Wiley & Sons, New York: (1982), page 259 written by Stephen L. Rosen; the contents of which are hereby incorporated by reference, for background and review.

[0090] It is also believed that the molecular weight of the polyimide chain can be degraded during the monoesterification process. A sufficiently high molecular weight polymer should be used to allow for some loss of MW during the esterification process yet still be within the desired range after completion. The molecular weights used in the present application are Number Average Molecular Weights and can be determined by GPC (Gel Permeation Chromatography).

[0091] Dispersing and “Sizing” Carbon Molecular Sieve Particles

[0092] In a preferred embodiment, the Carbon Molecular Sieve (CMS) particles are preconditioned at high temperature in a vacuum oven, for example at a temperature of about 300° C. under vacuum for at least 12 hours. After the preconditioning treatment, a desired quantity of CMS particles can be dispersed into a suitable solvent, preferably one which can be used to dissolve the desired organic polymer material that will be the continuous polymer phase in the eventual mixed matrix membrane. It is particularly preferred that the desired organic polymer is miscible in this solvent. The slurry is well agitated and mixed using any suitable method (e.g., shaker or two parallel rollers, etc.) for preferably between about 30 minutes to an hour. To enhance dispersal and homogeneity, a suitable ultrasonic sonicator can be applied to the slurry, for example, for approximately one minute. In a preferred embodiment, a long stainless steel rod from an ultrasonic high-frequency source generator is used to agitate the slurry. The sonication step breaks up conglomerations of CMS particles.

[0093] The CMS particles can optionally, but preferably, be “primed” (or “sized”) by adding a small amount of the desired matrix polymer or any suitable “sizing agent” that will be miscible with the organic polymer to be used for the matrix phase. Generally, this small amount of polymer or “sizing agent” is added after the CMS particles have been dispersed in a suitable solvent and sonicated by the ultrasonic agitator source. Optionally, a non-polar non-solvent, in which the polymer or “sizing agent” is insoluble, may be added to the dilute suspension to initiate precipitation of the polymer onto the carbon particles. The “primed” carbon particles may be removed through filtration and dried by any conventional means, for example in a vacuum oven, prior to re-dispersion in the suitable solvent for casting. The small amount of polymer or “sizing agent” provides an initial thin coating (i.e., boundary layer) on the CMS particle surface that will aid in making the particles compatible with the polymer matrix.

[0094] In a preferred embodiment, approximately 10% of total polymer material amount to be added for the final mixed matrix membrane is used to “prime” the CMS particles. The slurry is agitated and mixed for preferably between about 6 and 7 hours. After mixing, the remaining amount of polymer to be added is deposited into the slurry. The quantity of CMS particles and the amount of polymer added will determine the “loading” (or solid particle concentration) in the final mixed matrix membrane. Without limiting the invention, the loading of CMS particles is preferably from about 10 vol. % to about 60 vol. %, and more preferably, from about 20 vol. % to about 50 vol. %. To achieve the desired viscosity, the polymer solution concentration in the solvent is preferably from about 5 wt. % to about 25 wt. %. Finally, the slurry is again well agitated and mixed by any suitable means for about 12 hours.

[0095] This technique of “priming” the particles with a small amount of the polymer before incorporating the particles into a polymer film is believed to make the particles more compatible with the polymer film. It is also believed to promote greater affinity/adhesion between the particles and the polymers and may eliminate defects in the mixed matrix membranes. This “priming” technique is believed to be generally applicable to particles placed in polymer membranes, for example those membranes using zeolites rather than CMS particles. Accordingly, the invention described herein also includes a general method for “priming” particles for inclusion in polymer membranes.

[0096] Methods of Forming the Mixed Matrix Membrane

[0097] The mixed matrix membranes are typically formed by casting the homogeneous slurry containing CMS particles and the desired polymer, as described above. The slurry can be mixed, for example, using homogenizers and/or ultrasound to maximize the dispersion of the particles in the polymer or polymer solution. The casting process is preferably performed by three steps:

[0098] (1) pouring the solution onto a flat, horizontal surface (preferably glass surface),

[0099] (2) slowly and virtually completely evaporating the solvent from the solution to form a solid membrane film, and

[0100] (3) drying the membrane film.

[0101] To control the membrane thickness and area, the solution is preferably poured into a metal ring mold. Slow evaporation of the solvent is preferably effected by covering the area and restricting the flux of the evaporating solvent. Generally, evaporation takes about 12 hours to complete, but can take longer depending on the solvent used. The solid membrane film is preferably removed from the flat surface and placed in a vacuum oven to dry. The temperature of the vacuum oven is preferably set from about 50° C. to about 110° C. (or about 50° C. above the normal boiling point of the solvent) to remove remaining solvent and to anneal the final mixed matrix membrane.

[0102] The final, dried mixed matrix membrane can be further annealed above its glass transition temperature (T_(g)). The T_(g) of the mixed matrix membrane can be determined by any suitable method (e.g., differential scanning calorimetry). The mixed matrix film can be secured on a flat surface and placed in a high temperature vacuum oven. The pressure in the vacuum oven (e.g., Thermcraft® furnace tube) is preferably between about 0.01 mm Hg to about 0.10 mm Hg. Preferably, the system is evacuated until the pressure is 0.05 mm Hg or lower. A heating protocol is programmed so that the temperature reaches the T_(g) of the mixed matrix membrane preferably in about 2 to about 3 hours. The temperature is then raised to preferably about 10° C. to about 30° C., but most preferably about 20° C., above the T_(g) and maintained at that temperature for about 30 minutes to about two hours. After the heating cycle is complete, the mixed matrix membrane is allowed to cool to ambient temperature under vacuum.

[0103] The resulting mixed matrix membrane is an effective membrane material for separation of one or more gaseous components from gaseous mixtures including the desired component(s) and other components. In a non-limiting example of use, the resulting membrane has the ability to separate carbon dioxide from methane, is permeable to these substances, and has adequate strength, heat resistance, durability and solvent resistance to be used in commercial purifications. While not wishing to be bound to a particular theory, the molecular sieves are believed to improve the performance of the mixed matrix membrane by including selective holes/pores with a size that permits carbon dioxide to pass through, but either not permitting methane to pass through, or permitting it to pass through at a significantly slower rate. The molecular sieves should have higher selectivity for the desired gas separation than the original polymer to enhance the performance of the mixed matrix membrane. For the desired gas separation in the mixed matrix membrane, it is preferred that the steady-state permeability of the faster permeating gas component in the molecular sieves be at least equal to that of the faster permeating gas in the original polymer matrix phase. An advantage of the mixed matrix membranes described herein over membranes including primarily the continuous carbon-based molecular sieve membrane films and fibers is that they are significantly less brittle.

[0104] The membranes can be used in any convenient form such as sheets, tubes or hollow fibers. Hollow fibers can be preferred, since they provide a relatively large membrane area per unit volume. Sheets can be used to fabricate spiral wound modules familiar to those skilled in the art.

[0105] For flat-sheet membranes, the thickness of the mixed matrix selective layer is between about 0.001 and 0.005 inches, preferably about 0.002 inches. In asymmetric hollow fiber form, the thickness of the mixed matrix selective skin layer is preferably about 1000 Angstroms to about 5000 Angstroms. The loading of CMS particles in the continuous polymer phase is between about 10% and 60%, preferably about 20% to 50% by volume.

[0106] Mixed Matrix Membrane Enhancement Test For CMS Membranes

[0107] A test can be prepared to verify that the carbon molecular sieves formed via pyrolysis have been properly and successfully made to produce mixed matrix membranes with enhanced permeation properties. This test involves preparation of a sample mixed matrix membrane film using a test polymer and a specified loading of carbon molecular sieve particles, and comparing the CO₂/CH₄ permeation selectivity versus a membrane film of the same test polymer without added sieve. The CO₂/CH₄ permeation selectivity is determined by taking the ratio of the permeability of CO₂ over that of CH₄. The permeability of a gas penetrant i is a pressure- and thickness-normalized flux of the component through the membrane and is defined by the expression: $P_{i} = \frac{N_{i} \cdot l}{\Delta \quad p_{i}}$

[0108] where P_(i) is permeability of component i, is thickness the membrane layer, N_(l) is component i's flux (volumetric flow rate per unit membrane area) through the to membrane, and Δp_(l) is the partial pressure driving force of component i (partial pressure difference between the upstream to the downstream). Permeability is often expressed in the customary unit of Barrer (1 Barrer=10⁻¹⁰ cm³ (STP) .cm/cm².s.cm Hg). Permeability measurements can be made using a manometric, or constant volume, method. The apparatus for performing permeation measurements in films are described in O'Brien et al., J. Membrane Sci., 29, 229 (1986) and Costello et al., Ind. Eng. Chem. Res., 31, 2708 (1992), the contents of which are hereby incorporated by reference.

[0109] In the Mixed Matrix Enhancement Test, permeation tests of pure gases of CO₂ and CH₄ are performed on the mixed matrix membrane. The mixed matrix membrane film is separately tested with each gas using an upstream pressure of about 50 psia and a vacuum downstream. A temperature of about 35° C. is maintained inside the permeation system. Similar permeation tests of pure gases of CO₂ and CH₄ are performed on a prepared membrane film of the same test polymer without added sieve particles. To confirm that the carbon molecular sieves particles have been properly produced and prepared by the methods described herein, the mixed matrix membrane film should exhibit a CO₂/CH₄ selectivity enhancement in the Mixed Matrix Enhancement Test, of 10% or more over the CO₂/CH₄ selectivity of the pure test polymer membrane alone.

[0110] The method for forming the sample mixed matrix membrane for use in the Enhancement Test is as follows:

[0111] (1) The CMS fine particles are preconditioned at high temperature in a vacuum oven at a temperature of about 300° C. under vacuum for at least 12 hours. After the preconditioning treatment, these CMS particles can be used to prepare a sample mixed matrix membrane film. For the purpose of the Enhancement Test, the CMS particles are dispersed in the solvent dichioromethane (CH₂Cl₂).

[0112] (2) After dispersal in CH₂Cl₂, the CMS particles are sonicated in solution for about 1 minute with an ultrasonic rod in the vial and are well-mixed, as described previously. Large CMS particles in the slurry are separated from the fine particles by any conventional means, for example, decantation or centrifugation. After sonication and isolation of finer CMS particles, the CMS particles are ready for “priming” (or “sizing”) with the matrix polymer. For the purpose of the Enhancement Test, the polymer to be used for the matrix phase is Ultem® 1000 (GE Plastics). Its chemical structure is shown below.

[0113] Prior to use, the Ultem® 1000 polymer is dried at a temperature of about 100° C. under vacuum for at least 12 hours in a vacuum oven. For “priming” the CMS particles, typically 10 wt. % of the total amount of matrix polymer (Ultem® 1000) to be added to the slurry is used. For the Enhancement Test, it is desired to prepare the final slurry of CMS particles and polymer with the following properties: a weight ratio of Ultem® 1000 to CMS particles of about 4 to 1 (i.e., a “loading” of about 20 wt. % of CMS particles in the final mixed matrix membrane) and a slurry concentration of about 15 to about 20 wt. % solids (CMS particles and polymer) in CH₂Cl₂ solvent. After “priming” the CMS particles with Ultem® 1000, the slurry is well-mixed by any conventional means for about 12 hours. The remaining amount of Ultem® 1000 polymer is added to the slurry, and the final slurry is again well-mixed by any conventional means for about 12 hours.

[0114] (3) The polymer/CMS slurry is poured onto a flat, leveled, clean horizontal glass surface placed inside a controlled environment (e.g., plastic glove bag). To decrease the evaporation rate, the controlled environment is near-saturated with CH₂Cl₂ solvent. A stainless steel film applicator (Paul N. Gardner Co.) is used to draw/spread the CMS/polymer slurry to a uniform thickness. An inverted glass funnel was used to cover the solution. The tip of the funnel is covered with lint-free tissue paper to further control the evaporation rate. The solvent from the polymer film slowly evaporates over about a 12-hour time period. The dried film approximately has a thickness of about 30 to about 60 microns. After drying, the membrane film is annealed at a temperature of about 100° C. for about 12 hours in vacuum.

[0115] (4) To perform the Enhancement Test, permeability measurements of the flat mixed matrix membrane films are required. The measurements can be made using a manometric, or constant volume, method. The apparatus is described in references previously cited in this section. A sample film area from final mixed matrix film is masked with adhesive aluminum masks having a circular, pre-cut, exposed area for permeation through the membrane. The masked membrane can be placed in a permeation cell and the permeation system. Both the upstream and downstream sections of the permeation system are evacuated for about 24 hours to 48 hours to remove (“degas”) any gases or vapors sorbed into the membrane. Permeation tests of the membrane can be performed by pressurizing the upstream side with the desired gas at the desired pressure. The permeation rate can be measured from the pressure rise of a pressure transducer and using the known downstream (permeate) volume. Following the permeation testing of a given gas, both the upstream and downstream sections are evacuated for at least 12 hours before permeation testing of the next gas.

[0116] With the above procedure, the CO₂ and CH₄ permeabilities are measured for the test mixed matrix membrane and the pure test polymer (Ultem® 1000). The CO₂/CH₄ selectivity of the mixed matrix membrane is compared to the CO₂/CH₄ selectivity of the pure test polymer (Ultem® 1000) alone. A CO₂/CH₄ selectivity enhancement of 10% or more should be observed in the mixed matrix membrane film.

[0117] Separation Systems Including the Membranes

[0118] The preferred form membrane used in the present invention is hollow fibers. However, the membranes may take any form known in the art. Some other membrane shapes include spiral wound, pleated, flat sheet, or polygonal tubes. Multiple hollow fiber membrane tubes are preferred for their relatively large fluid contact area. The contact area may be further increased by adding additional tubes or tube contours. Contact may also be increased by altering the gaseous flow by increasing fluid turbulence or swirling.

[0119] The preferred glassy materials that provide good gas selectivity, for example carbon dioxide/methane selectivity, tend to have relatively low permeabilities. A preferred form for the membranes is, therefore, integrally skinned or composite asymmetric hollow fibers, which can provide both a very thin selective skin layer and a high packing density, to facilitate use of large membrane areas. Hollow tubes can also be used.

[0120] Sheets can be used to fabricate a flat stack permeator that includes a multitude of membrane layers alternately separated by feed-retentate spacers and permeate spacers. The layers can be glued along their edges to define separate feed-retentate zones and permeate zones. Devices of this type are described in U.S. Pat. No. 5,104,532, the contents of which is hereby incorporated by reference.

[0121] The membranes can be included in a separation system that includes an outer perforated shell surrounding one or more inner tubes that contain the mixed matrix membranes. The shell and the inner tubes can be surrounded with packing to isolate a contaminant collection zone.

[0122] In one mode of operation, a gaseous mixture enters the separation system via a containment collection zone through the perforations in the outer perforated shell. The gaseous mixture passes upward through the inner tubes. As the gaseous mixture passes through the inner tubes, one or more components of the mixture permeate out of the inner tubes through the selective membrane and enter the containment collection zone.

[0123] The membranes can be included in a cartridge and used for permeating contaminants from a gaseous mixture. The contaminants can permeate out through the membrane, while the desired components continue out the top of the membrane. The membranes may be stacked within a perforated tube to form the inner tubes or may be interconnected to form a self-supporting tube.

[0124] Each one of the stacked membrane elements may be designed to permeate one or more components of the gaseous mixture. For example, one membrane may be designed for removing carbon dioxide, a second for removing hydrogen sulfide, and a third for removing nitrogen. The membranes may be stacked in different arrangements to remove various components from the gaseous mixture in different orders.

[0125] Different components may be removed into a single contaminant collection zone and disposed of together, or they may be removed into different zones. The membranes may be arranged in series or parallel configurations or in combinations thereof depending on the particular application.

[0126] The membranes may be removable and replaceable by conventional retrieval technology such as wire line, coil tubing, or pumping. In addition to replacement, the membrane elements may be cleaned in place by pumping gas, liquid, detergent, or other material past the membrane to remove materials accumulated on the membrane surface.

[0127] A gas separation system including the membranes described herein may be of a variable length depending on the particular application.

[0128] The gaseous mixture can flow through the membrane(s) following an inside-out flow path where the mixture flows into the inside of the tube(s) of the membranes and the components which are removed permeate out through the tube. Alternatively, the gaseous mixture can flow through the membrane following an outside-in flow path.

[0129] In order to prevent or reduce possibly damaging contact between liquid or particulate contaminates and the membranes, the flowing gaseous mixture may be caused to rotate or swirl within an outer tube. This rotation may be achieved in any known manner, for example using one or more spiral deflectors. A vent may also be provided for removing and/or sampling components removed from the gaseous mixture.

[0130] The membranes are preferably durable, resistant to high temperatures, and resistant to exposure to liquids. The materials may be coated, ideally with a polymer, to help prevent fouling and improve durability. Examples of suitable polymers include those described in U.S. Pat. Nos. 5,288,304 and 4,728,345, the contents of which are hereby incorporated by reference. Barrier materials may also be used as a pre-filter for removing particulates and other contaminants which may damage the membranes.

[0131] Methods of Forming Hollow Fibers

[0132] Hollow fibers can be formed, for example, by extruding a polymer/molecular sieve mixture through a tubular capillary nozzle with a core fluid used for the purpose of retaining the hollow fiber shape. These fibers typically have the diameter of a human hair and offer the advantage of maximizing the surface area per unit volume. Industrial hollow fiber membrane modules typically contain hundreds of thousands of individual hollow fibers. Specifically, to maximize productivity, the hollow fibers typically include an ultrathin (<2000 Angstroms) “skin” layer on a porous support. Gas separation is accomplished through this selective “skin.” This outer “skin” layer may be supported on the same polymer to form an integrally skinned asymmetric hollow fiber membrane. The most advanced membranes have an asymmetric sheath with the selective skin supported on an inexpensive porous core layer (different polymer) to form a composite hollow fiber membrane. This type of device is described in U.S. Pat. No. 5,085,676, the contents of which are hereby incorporated by reference.

[0133] Hollow fibers can be employed in bundled arrays potted at either end to form tube sheets and fitted into a pressure vessel thereby isolating the insides of the tubes from the outsides of the tubes. Devices of this type are known in the art. Preferably, the direction of flow in a hollow fiber element will be counter-current rather than co-current or even transverse. Such counter-current flow can be achieved by wrapping the hollow fiber bundle in a spiral wrap of flow-impeding material. This spiral wrap extends from a central mandrel at the center of the bundle and spirals outward to the outer periphery of the bundle. The spiral wrap contains holes along the top and bottom ends whereby gas entering the bundle for tube side flow at one end is partitioned by passage through the holes and forced to flow parallel to the hollow fiber down the channel created by the spiral wrap. This flow direction is counter-current to the direction of flow inside the hollow fiber. At the bottom of the channels the gas re-emerges from the hollow fiber bundle through the holes at the opposite end of the spiral wrap and is directed out of the module.

[0134] Purification Process

[0135] A mixture containing gases to be separated, for example carbon dioxide and methane, can be enriched by a gas-phase process through the mixed matrix membrane, for example, in any of the above-configurations. The preferred conditions for enriching the mixture involve using a temperature between about 25° C. and 200° C. and a pressure of between about 50 psia and 5000 psia. These conditions can be varied using routine experimentation depending on the feed streams. Other gas mixtures can be purified with the mixed matrix membrane in any of the above configurations. For example, applications include enrichment of air by nitrogen or oxygen, nitrogen or hydrogen removal from methane streams, or carbon monoxide from syngas streams. The mixed matrix membrane can also be used in hydrogen separation from refinery streams and other process streams, for example from the dehydrogenation reaction effluent in the catalytic dehydrogenation of paraffins. Generally, the mixed matrix membrane may be used in any separation process with gas mixtures involving, for example, hydrogen, nitrogen, methane, carbon dioxide, carbon monoxide, helium, and oxygen. The gases that can be separated are those with kinetic diameters that allow passage through the molecular sieves. The kinetic diameter (also referred to herein as “molecular size”) of gas molecules are well known, and the kinetic diameters of voids in molecular sieves are also well known, and are described, for example, in D. W. Breck, Zeolite Molecular Sieves, Wiley (1974), the contents of which are hereby incorporated by reference.

[0136] Additional Purification

[0137] If additional purification is required, the product in the permeate stream can be passed through additional membranes, and/or the product can be purified via distillation using techniques well known to those of skill in the art. Typically, membrane systems may consist of many modules connected in various configurations (See, for example, Prasad et al., J. Membrane Sci., 94, 225-248 (1994), the contents of which are hereby incorporated by reference for background and review). Modules connected in series offer many design possibilities to purify the feed, permeate, and residue streams to increase the separation purity of the streams and to optimize the membrane system performance.

[0138] The effectiveness of the polymer membrane for gas separations can be determined. As discussed above the membrane to be commercially viable must have high permebility of at least one component in combination with excellent selectivity. Preferably the crosslinked polyimide polymer; having a CO₂ permeability of at least 20 barrers and a CO₂/CH₄ selectivity of greater than 30. The permeability and selectivity of the membrane is measured at 35 degrees C. and a pressure of 100 psia.

[0139] Methodology of Fiber Module Construction

[0140] For laboratory or commercial use, a suitable plurality of the fibers is bundled together to form a separation unit. The number of fibers bundled together will depend on fiber diameters, lengths, and porosities and on desired throughput, equipment costs, and other engineering considerations understood by those in the chemical engineering arts.

[0141] The fibers are held together by any conventional means. This assembly is then typically disposed in a pressure shell such that one end of the fiber assembly extends to one end of the pressure shell and the opposite end of the fiber assembly extends to the opposite end of the pressure shell. The fiber assembly is then fixably or removably affixed to the pressure shell by any conventional method to form a pressure tight seal.

[0142] The unit is then operated, e.g., as a shell-tube heat exchanger, where the feed is passed to either the shell or tube side at one end of the assembly and the product is removed from the other end. For maximizing high-pressure performance, the high-pressure feed is typically fed to the shell side of the assembly. At least a portion of the CO₂ in the feed passes through the membrane to the tube side, i.e., inside the membranes. CO₂ depleted feed is then removed from the opposite end of the shell side of the assembly. Any conventional recycle scheme may be optionally used to optimize a desired purity level.

[0143] In order to perform permeation tests, for example, a test module consisting of a single fiber is constructed, as shown in FIG. 2. Details of fabricating the module are given in the Illustrated Embodiments section below.

[0144] Operating Conditions

[0145] The process is operated with a feed pressure of from about 20 psia to about 4000 psia, preferably at least about 50 psia, and more preferably from about 200 psia to about 1000 psia. The feed temperature can be ambient or can be selected to optimize the selectivity.

[0146] Methodology of Single Fiber Module Construction

[0147] Reference is made to FIG. 6. In order to perform permeation tests, a module 200 consisting of a single fiber 205 was constructed. The module 200 is fabricated from two stainless steel (316) Swagelok® ¼-inch tees 210, stainless steel ¼-inch tubing and nuts, two brass NPT ¼-inch female-tube adapters 215, two brass NPT ¼-inch male-tube adapters 220, and two brass Swagelok® ¼-inch nuts. The hollow fiber membrane 205 is threaded through the module housing, so that a length of carbon fiber extends on each end. The ends of the module are then plugged with Stycast® 2651 epoxy 225 (from Emerson-Cuming Company) cured for overnight. The ends of the membrane 205 are snapped off after the epoxy hardens.

[0148] Methodology of Membrane Testing System

[0149] Reference is made to FIGS. 6 and 7. The permeation testing for the fibers 205 was performed with single-fiber test modules 200. Gas transport through the membranes was examined with a pressure-rise permeation testing system 300. The system permitted high-pressure testing of mixed feed gas and sampling of gas streams with a gas chromatograph. The module 200 was attached in a shell feed method of operation. Mixed feed gas 305 from a compressed gas cylinder 310 was supplied on the shell-side of a single-fiber test module 200. The module 200 and ballast volumes were placed in a circulating water bath 315 to control and maintain a constant temperature.

[0150] Vacuum was pulled on both the shell- and bore-side of the hollow fiber membrane 205 first for overnight before testing. Permeate at the two ends from the bore-side of the fiber was pulled by vacuum through a downstream sample volume. The permeation rate was measured from the pressure rise of a Baratron® pressure transducer 320 over time after closing the valve to vacuum. The pressure rise was plotted on chart recorder. The compositions of all the streams can be determined by a gas chromatograph. Individual gas fluxes were then calculated. The plumbing of the system consisted of stainless steel (316) Swagelok® ¼-inch and ⅛-inch fittings and tubing, Whitey® and Nupro® valves with welded elements. The system is rated for over 1500 psia pressure.

[0151] The present invention will be better understood with reference to the following non-limiting examples.

EXAMPLES

[0152] The present examples are intended to help illustrate the process of the present invention and are not meant to limit the scope of the application.

Example 1 Synthesis of Monoester via Activated Carboxylic Acid

[0153] The reactivity of the diols strongly depends on their structure. Due to the electron releasing effect of the methylene groups the reactivity of diols is increasing with increasing chain length. For example, 1,4 butanediol>1,3-propane diol>ethylene glycol. Synthesis of the monoester over activated carboxylic acid derivatives as shown in FIG. 2 might be especially interesting for less reactive crosslinking agents.

[0154] The monoesterification reaction was carried out as follows: the DABA-copolyimide is dissolved in THF (10 wt %) under nitrogen atmosphere and 2 times of the stoichiometric amount of thionyl chloride is added. The reaction is heated to reflux and the excess of thionyl chloride and THF is distilled out of the reaction solution. The residual copolyimide acid chloride (brown crystals) was stored under vacuum at low temperature (50° C) overnight. The acid chloride was dissolved in THF and dropped slowly to an excess of glycol (70 times excess) dissolved in THF. Elevated temperature was necessary because phase separation tends to occur during this reaction step. It was found that the acid chloride showed a much lower solubility in THF compared to the DABA copolyimide, so using NMP as a solvent for the second step of the reaction might be useful.

[0155] With the procedure described above it is assumed that a certain amount of diester is already obtained during the monoester formation. This is indicated by the fact that a 10 wt % solution of the monoester (over the acid chloride route) in NMP showed a significant higher viscosity than monoester solutions obtained over the self catalyzed reaction. It was also obvious that the mechanical properties drastically improved. Starting with a material forming very brittle films, probably due to low molecular weight, over the acid chloride route films with high flexibility were obtained. Therefore, the synthesis of monoester over the acid chloride route can be a valuable method for building up molecular weight, which itself leads high viscosity and can help in the process of hollow fiber spinning.

Example 2 Self Catalyzed Monoesterification Reaction

[0156] Some of the diols such as 1,4 butanediol have been found to form the monoester without the use of a catalyst. For the self-catalyzed reaction, DABA-copolyimides are dissolved in dry NMP (15-17 wt %) and 70 times excess of diol is added. The reaction mixture is stirred for 12 hours at 130° C. under nitrogen purge. Precipitation, blending and filtration lead to fluffy particles of monoester which are dried at 70° C. under vacuum.

Example 3 Acid Catalyzed Monoesterification Reaction

[0157] For the acid catalysed reaction, per 2 g of polymer 1 mg of p-Toluene sulfonic acid was added. The procedure for the reaction was the same as for the self-catalyzed reaction.

Example 4 Conversion of the Monoesterification Reaction

[0158] We have found that ¹H-NMR is a useful method to show the conversion which can be reached in the monoesterification reaction. This should be explained on two examples. FIG. 4 shows the ¹H NMR of 6FDA-DAM/DABA 3:2 non-crosslinked in DMSO-D6. The presence of the DABA units can be proven by comparing the ratio of all aromatic protons and aliphatic protons (3 methyl groups of DAM). For this case we found:

[0159] After the self-catalyzed monoesterification reaction with 1 ,4-butanediol and low temperature drying of the monoester (70° C. under vacuum), again ¹H NMR was performed. The spectrum is shown in FIG. 4. For the monoester-NMR we can calculate the conversions of the reaction by the ratio of aromatic protons and aliphatic protons of the methylene group next to the ester group. We can check the calculations also by the ratio of DAM-methyl protons and the methylene group next to the ester group.

[0160] From the spectrum obtained for the monoesterification reaction it can be concluded that nearly complete conversions can be obtained with 1,4-butanediol using the self-catalyzed reaction conditions.

[0161] As already mentioned we assume that the ethylene glycol is less nucleophilic than the butylene glycol. It has been found that using ethylene glycol in a self-catalyzed monoesterification reaction, the conversions seems to be much lower. The ¹H-NMR of the 6FDA-DAM/DABA 2:1 ethylene glycol monoester is shown in FIG. 5

[0162] Table 1 summarizes the results for the conversions obtained with copolyimides having different DAM/DABA compositions. Thereby different methods for synthesizing the monoester copolyimide were investigated. The conversion of the reactions was indepently calculated from the ratio of aromatic protons (without the aromatic DAM proton) and the methylene protons next to the ester group as well as from the ratio of the aliphatic DAM methyl protons and the methylene protons next to the ester. The follwing conclusions can be drawn:

[0163] The monoesterification reaction can be catalyzed by protons. Therefore it is obvious that with increasing DABA content of the copolyimide structure higher conversion rates are obtained. The DAM/DABA 4:1 with butanediol shows a conversion of less than 50% whereas for the DAM/DABA 3:2 a conversion of over 90% was obtained (self catalyzed). Ethylene glycol generally has a lower nucleophilic character than butanediol, the conversion for a DAM/DABA 2:1 composition is rather low (less than 40%) although a high number of protons are present due to the high DABA content.

[0164] For DAM/DABA 4:1 monoesterification with ethylene glycol very low conversion was expected (at least less than 40%) in the self-catalyzed reaction due to the low DABA content. By adding p-Toluene sufonic acid to the monoesterification reaction conversions of more than 60% preferably more than 80% can be reached.

[0165] The acid chloride groups are highly reactive groups, therefore conversions are over 95% for the monoester synthesis over the acid chloride route. This method might be important for the monoesterification reactions using multifunctional crosslinking agents and DABA structures with low DABA contents. TABLE 1 Calculated Conver- sion based Calculated on DAM- Conversion based CH₃ on Aromatics protons/ Ratio: (without DAM/ methylene Copolyimide Aromatics (total)/ methylene protons protons Monoester DAM-CH3 protons (on ester) (on ester) DAM/DABA 4:1 theoretical: 22 23 Butanediol 1.03 Self-catalyzed experimental: 1.08 DAM/DABA 2:1 theoretical: 38 40 Ethylene glycol 1.28 Self-catalyzed experimental: 1.23 DAM/DABA 3:2 theoretical: 94 98 Butanediol 1.44 Self-catalyzed experimental: 1.50 DAM/DABA 3:2 theoretical: 97 98 Butanediol 1.44 Over acid experimental: chloride 1.49

Example 5 Plasticization Resistance

[0166] In order to show CO₂ plasticization resistance, pure CO₂ permeation experiments have been performed with the 6FDA-DAM/DABA 3:2 film crosslinked with 1,4 butanediol at 140° C. To determine the CO₂ plasticization the CO₂ permeability is measured at increasing CO₂ pressure. The CO₂ pressure was held at a given pressure for 24 hours then the CO₂ permeability was measured. The CO₂ pressure was then held for an additional 24 hours and again measured. A substantial increase in the CO₂ permeability indicates plasticization. Results of plasticization test are shown in FIG. 8. FIG. 8 shows that the crosslinked material has surprising resistance to plasticization.

Comparative Example 6 Plasticization Resistance of Uncrosslinked Film

[0167] To contrast the plasticization resistance of a crosslinked membrane (of Example 5), an uncrosslinked film was tested under similar conditions to Example 5. The results of this test are shown in FIG. 9. FIG. 9 shows a substantial increase in the CO₂ permeability indicating plasticization. 

What is claimed is:
 1. A hollow fiber polymer membrane, comprising: a) a crosslinked polymer continuous phase; and b) a molecular sieve material dispersed within said continuous phase; wherein said membrane has a CO₂ permeability of at least 20 barrers and a CO₂/CH₄ selectivity of greater than 30, at 35 degrees C. and a pressure of 100 psia.
 2. A hollow fiber mixed matrix polymer membrane, comprising: a) a continuous phase polymer comprising a polyimide having crosslinkable sites; and b) a molecular sieve material dispersed within said continuous phase polymer; wherein the ratio of crosslinkable sites to imide groups is between 3:8 and 1:16.
 3. A hollow fiber mixed matrix polymer membrane material, comprising: a molecular sieve dispersed within a continuous polymer phase wherein said continuous polymer phase comprises a polyimide polymer made from the monomers A+B+C; where A is a dianhydride of the formula;

where X₁ and X₂ are independently a halogenated alkyl group, phenyl or halogen; where R₁, R₂, R₃, R₄, R₅, and R₆ are independently H, alkyl, or halogen; where B is a diamino cyclic compound without a carboxylic acid functionality; where C is a diamino cyclic compound with a carboxylic acid functionality; and wherein the ratio of B to C is between 1:4 and 8:1.
 4. The hollow fiber polymer membrane of claim 1 wherein the molecular sieve material dispersed within said continuous phase has an average particle size of less than about 1 micron.
 5. The hollow fiber polymer membrane material of claim 3 where X₁ and X₂ are CF₃.
 6. The hollow fiber polymer membrane material of claim 3 where R₁, R₂, R₃, R₄, R₅, and R₆ are H.
 7. The hollow fiber polymer membrane material of claim 3 wherein the dianhydride is 6FDA.
 8. The hollow fiber polymer membrane material of claim 3 wherein C is DABA.
 9. The hollow fiber polymer membrane material of claim 3 wherein B is a diamino aromatic compound.
 10. The hollow fiber polymer membrane material of claim 3 wherein B is a diamino benzene compound having one or more methyl groups attached to the benzene ring.
 11. The hollow fiber polymer membrane material of claim 3 wherein the ratio of B to C is between 17:3 and 3:2.
 12. The hollow fiber polymer membrane material of claim 3 wherein the ratio of B to C is between 17:3 and 3:1.
 13. The hollow fiber polymer membrane material of claim 3 wherein said membrane is subjected to esterification conditions in the presence of a diol selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,2 butanediol, benzenedimethanol, and 1,3 butanediol to form a hollow fiber polymer membrane monoester.
 14. The hollow fiber polymer membrane material of claim 13 wherein at least 60% of the carboxylic acid functionality is converted to a monoester.
 15. The hollow fiber polymer membrane material of claim 13 wherein the hollow fiber membrane monoester is subjected to transesterification conditions to form a crosslinked hollow fiber polymer membrane.
 16. The hollow fiber polymer membrane of claim 1 wherein the molecular sieve material dispersed within said continuous phase has an average particle size of less than about 0.1 micron.
 17. The hollow fiber polymer membrane material of claim 3 wherein B is diamino durene.
 18. The hollow fiber polymer membrane of claims 1, 2 and 3 wherein the molecular sieve is a zeolite.
 19. The hollow fiber polymer membrane of claims 1, 2 and 3 wherein the molecular sieve is carbon molecular sieve.
 20. The hollow fiber polymer membrane of claims 1, 2 and 3 wherein the molecular sieve is a aluminophosphate zeolite.
 21. The hollow fiber polymer membrane of claims 1, 2 and 3 wherein the molecular sieve is a borosilicate.
 22. The hollow fiber polymer membrane of claims 1, 2 and 3 wherein the molecular sieve is a SAPO.
 23. A method of making a crosslinked hollow fiber membrane, comprising: preparing a continuous phase polyimide polymer comprising a predetermined quantity of crosslinkable sites and a molecular sieve material dispersed within said continuous phase polymer; forming a hollow fiber from said continuous phase polyimide polymer; treating the hollow fiber with a diol selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,2 butanediol, and 1,3 butanediol, at esterification conditions, to form a monoesterified hollow fiber; and subjecting the monoesterified hollow fiber to transeesterification conditions to form a crosslinked hollow fiber membrane.
 24. A method of making a crosslinked hollow fiber membrane, comprising: preparing a polyimide polymer comprising a predetermined quantity of crosslinkable sites and a molecular sieve material dispersed within said continuous phase polymer; treating the polyimide polymer with a diol selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,2 butanediol, and 1,3 butanediol, at esterification conditions, to form a monoesterified membrane material; forming a monoesterified hollow fiber from the monoesterified membrane material; and subjecting the monoesterified hollow fiber to transesterification conditions to form a crosslinked hollow fiber membrane.
 25. The hollow fiber polymer membrane material of claim 13 wherein at least 80% of the carboxylic acid functionality is converted to a monoester. 